醋酸乙烯氢甲酰化反应工艺中的区域选择性研究  

Investigation on regioselectivity of hydroformylation of vinyl acetate

作　　者：徐向亚[1] 冯华升[1] 赵思源[1] 邵芸[1] 刘红梅[1] 刘东兵[1] Xu Xiangya;Feng Huasheng;Zhao Siyuan;Shao Yun;Liu Hongmei;Liu Dongbing(Beijing Research Institute of Chemical Industry,SINOPEC,Beijing 100013,China)

机构地区：[1]中国石油化工股份有限公司北京化工研究院

出　　处：《工业催化》2019年第6期80-84,共5页Industrial Catalysis

基　　金：中国石油化工股份有限公司项目(G6001-17zs0430)

摘　　要：醋酸乙烯氢甲酰化是带有多官能团的烯烃氢甲酰化反应,即其主要产物2-乙酰氧基丙醛和3-乙酰氧基丙醛具有双官能团酯基和醛基,经氢化水解可以得到1,2-丙二醇和1,3-丙二醇,或者经氧化水解得到乳酸和3-羟基丙酸等重要的工业原料及产品。对HRh(CO)(PPh3)3催化醋酸乙烯氢甲酰化反应进行研究,发现其对醋酸乙烯氢甲酰化反应具有良好的催化活性,且对生成2-乙酰氧基丙醛具有良好的选择性。同时对ROPAC(乙酰丙酮三苯基膦羰基铑)催化体系进行考察,发现使用DIOP(邻苯二甲酸二异辛酯)配体并降低反应温度至100℃时,可以增加3-乙酰氧基丙醛选择性。Hydroformylation of vinyl acetate is reaction of olefins with multi-functional groups.Its main products are 2-acetoxypropanal and 3-acetoxypropanal having bifunctional groups of esters and aldehydes.Then,1,2-propanediol and 1,3-propanediol can be obtained by hydrogenation hydrolysis,or lactic acid and 3-hydroxypropionic acid can be obtained by oxidation hydrolysis.In this paper,the hydroformylation of vinyl acetate catalyzed by HRh(CO)(PPh 3 ) 3 was studied.It was found that HRh(CO)(PPh 3 ) 3 had good catalytic activity for the hydroformylation of vinyl acetate and good selectivity for the formation of 2-acetoxypropanal.At the same time,investigation on the catalytic system of ROPAC found that selectivity of 3-acetoxypropanal could be increased when DIOP ligand was invited and reaction temperature lowered to 100 ℃.

关 键 词：有机化学工程 醋酸乙烯 氢甲酰化 区域选择性 Rh催化剂 膦配体 

分 类 号：TQ426.94[化学工程] TQ223.162